CN107732245A - A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery - Google Patents
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery Download PDFInfo
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- CN107732245A CN107732245A CN201710984589.7A CN201710984589A CN107732245A CN 107732245 A CN107732245 A CN 107732245A CN 201710984589 A CN201710984589 A CN 201710984589A CN 107732245 A CN107732245 A CN 107732245A
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- composite negative
- lithium battery
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 105
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 39
- -1 graphite alkene Chemical class 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000000428 dust Substances 0.000 claims abstract description 16
- 230000006641 stabilisation Effects 0.000 claims abstract description 14
- 238000011105 stabilization Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 229910052708 sodium Inorganic materials 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 23
- 229920002472 Starch Polymers 0.000 claims description 22
- 239000008107 starch Substances 0.000 claims description 22
- 235000019698 starch Nutrition 0.000 claims description 22
- 229910052593 corundum Inorganic materials 0.000 claims description 20
- 239000010431 corundum Substances 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229930006000 Sucrose Natural products 0.000 claims description 15
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000005720 sucrose Substances 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 abstract description 8
- 239000010406 cathode material Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 238000005255 carburizing Methods 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the preparing technical field of lithium cell cathode material, there is provided a kind of preparation method of hard carbon/graphene composite negative pole for lithium battery.After organic polymer is carried out stabilization processes by this method, it is mixed in sheet graphene in organic solvent, temperature reaction after supersound process, obtains the composite precursor of hard carbon/graphene.Then presoma is mixed with nanometer spherical metal dust, high temperature thermal decomposition is carried out under gas shield, formed spherical hard carbon and be coated on the surface of nanometer spherical metal dust, and be clipped between lamellar graphite alkene, produce hard carbon/graphene composite negative pole.Compared with conventional method, the electrode capacity of hard carbon/graphene composite negative pole prepared by the present invention is big, its lithium battery assembled, stability is preferable, cycle performance preferably overcomes the defects of loss of general anode material reversible specific capacity is larger, whole preparation process is easy to control, product appearance and stable performance, and cost performance is higher.
Description
Technical field
The invention belongs to the preparing technical field of lithium cell cathode material, there is provided a kind of hard carbon/stone for lithium battery
The preparation method method of black alkene composite negative pole material.
Background technology
Lithium metal has light weight, electrode potential negative and many advantages, such as specific capacity is high, and field of batteries is introduced into 1958,
As the chargeable lithium battery that material is made is higher than energy, specific power is big, and the business for entering lithium primary battery in 1970 is researched and developed
Stage, since nineteen ninety, with the innovation of positive electrode, negative material and electrolyte, can charge and discharge serondary lithium battery constantly send out
Open up and realize commercialization.Nowadays the sustainable development of lithium battery technology is constantly improving human lives.
Lithium-ion-power cell had wide range of applications because of the advantages that its energy is high, in light weight, green pollution-free, its
Application field includes digital product, household electrical appliance, electric tool, electric automobile, Aeronautics and Astronautics and weaponry etc..Wherein I
State's lithium dynamical battery mainly includes power tool battery, battery of electric bicycle and batteries of electric automobile etc., with technology not
Disconnected progress, security of lithium-ion-power cell improve constantly, and lithium battery monomer capacity is increasing, preceding in order to adapt to new energy vapour
The lithium-ion-power cell of the development of car, quick charge and big multiplying power discharging turns into the focus of research and development.
The research of performance of lithium ion battery, it is very heavy to choose the good both positive and negative polarity active material selection of chemical property
Will.Wherein, the negative pole of lithium ion battery is mixed by active carbon material or non-carbon material, adhesive and additive, at present
The still carbon materials that negative active core-shell material mainly uses, such as graphite, soft carbon, hard carbon.
Wherein, graphite because its good conductivity, crystallinity it is high, there is good layer structure, reversible specific capacity is reachable
More than 300mah/g, Chen et al. have invented a kind of ultrafine graphite cathode material, use high-end graphite produce after auxiliary material for
The primary raw material of the product, make particle size reduction on the basis of 5um by attritioning, then be surface-treated, by 1200 ° of charings
Afterwards, then 3000 ° of graphitization sintering are carried out, then carries out coarse crushing sieving and acquire corresponding product, this product has good conductive work
With resistance is low, and processing characteristics is good in lithium ion battery production process, and stable performance is cost-effective, is rate lithium battery
Optimal negative material.But shortcoming is that graphite material structural stability is poor, the poor compatibility with electrolyte, and Li ions have at it
Diffusion velocity in sequence layer structure is slow, causes the material to be unable to high rate charge-discharge.And soft carbon crystallinity is low, crystallite dimension
Small, interplanar distance is big, good with compatibility of electrolyte, but first charge-discharge irreversible capacity is preferable, and comfortable voltage is low, application
It is smaller.
Therefore, the exploitation of hard carbon material attracts attention, because of higher capacity possessed by its random sequence, low cost and excellent
Cycle performance turns into the focus of lithium cell cathode material research.A kind of power energy-storage battery of Ji et al. disclosure of the invention is born with hard carbon
Pole material and preparation method thereof, including：1）Carbon base body is rubber, fiber, resin high molecular polymer or its mixture, carries out one
After secondary curing process, crush, be classified to grain diameter below 300 μm；2）One-step solidification product adds crosslinking agent, is crosslinked
After polymerisation, secondary solidification is carried out, crushing and classification to grain diameter is below 250 μm；3）Secondary cured product and curing agent,
After dopant mixing, solidified three times, crushed；4）Cured product is sufficiently mixed with coating three times, is carried out at four solidifications
Reason, crush；5）Four cured products carry out a charing process in atmosphere of inert gases, crush, are classified to grain diameter and exist
Less than 150 μm；6）Carbonizing production continues secondary charing process after insulation, crushes, is classified to grain diameter and exists
Less than 30 μm.But hard carbon material reversible specific capacity loss in first charge-discharge is larger, and can under oxygen, carbon dioxide environment
Inverse specific capacity degradation.Therefore there is important actual meaning to improve its reversible specific capacity for hard carbon structure and surface modification
Justice.
The content of the invention
The defects of reversible specific capacity loss is larger in first charge-discharge in cathode of lithium battery for hard carbon material, proposes one
Kind for lithium battery hard carbon/graphene composite negative pole preparation method, by by sheet graphene and organic carbon source
Such as starch, sucrose are dispersed in organic solvent, and hydro-thermal method synthesizing graphite alkene/hard carbon presoma is used after being sufficiently stirred,
Presoma is well mixed in tube furnace the progress high temperature burning under inert gas shielding with nanometer spherical metal dust after drying
Knot, the active product sintered out have sandwich construction, and spherical hard carbon coats metal dust, is clipped between lamellar graphite alkene.
The preparation method of the present invention, it is poor to solve general lithium battery graphite cathode material structural stability, with electrolyte
Poor compatibility, diffusion velocity is slow, the shortcomings of causing the material to be unable to high rate charge-discharge, while avoids hard carbon material first
The problem of reversible specific capacity loss is larger in discharge and recharge.
Concrete technical scheme of the present invention is as follows：
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it is characterized in carrying out organic carbon source surely
After determining processing, it is mixed in sheet graphene in organic solvent, temperature reaction after supersound process, obtains hard carbon/graphene
Composite precursor；Then presoma is mixed with nanometer spherical metal dust, high warm point is carried out under inert gas shielding
Solution, forms spherical hard carbon and is coated on the surface of nanometer spherical metal dust, and is clipped between lamellar graphite alkene, produces hard carbon/stone
Black alkene composite negative pole material；What is prepared comprises the following steps that：
（1）Organic carbon source is placed in corundum crucible, then crucible is placed in tube type resistance furnace, is protected in atmosphere of inert gases
Under, temperature is raised, the stabilization processes of certain time are carried out to organic carbon source, make dehydration occurs between its molecule；
（2）By sheet graphene and step（1）The organic carbon source of processing is added in organic solvent, is sufficiently stirred scattered equal
It is even, the mixed liquor of a certain amount of sodium metaaluminate and sodium hydroxide is added, 1 ~ 2h is aged at room temperature, then moves into polytetrafluoroethyl-ne
Alkene is in the pyroreaction kettle of substrate, is first ultrasonically treated certain time, then is gradually heating to reaction temperature, and is incubated a timing
Between, it is swelled organic carbon source, then filtered, methanol solution is washed and dried, and obtains hard carbon/graphene presoma；
（3）By step（2）The presoma of gained is well mixed with nanometer spherical metal dust in V-Mixer, is then charged into
In corundum crucible, under the protection of atmosphere, in being heated at high temperature in tube furnace, hard carbon presoma is thermally decomposed, formed
Spherical hard carbon is coated on the surface of nano metal powder, and is clipped between lamellar graphite alkene, produces hard carbon/graphene composite negative
Material.
Preferably, step（1）The organic carbon source is starch or sucrose.
Preferably, step（1）The treatment temperature is 200 ~ 240 DEG C, processing time 10-15min.
Preferably, step（2）The number of plies of the sheet graphene is its matter with the organic carbon source of processing less than 5 layers
Amount is than being 1:3~1:2.
Preferably, step（2）The organic solvent is methanol, ethanol or glycerine, and its addition is graphene and processing
1.2 ~ 1.5 times of organic carbon source quality summation.
Preferably, step（2）In the mixed liquor, the mass concentration of sodium metaaluminate is 0.5 ~ 1%, the quality of sodium hydroxide
Concentration is 1 ~ 2%, and the addition quality of mixed liquor is the 1/4 ~ 1/3 of organic solvent quality.
Preferably, step（2）The power of the supersound process is 80kHz, and the time is 40 ~ 60min.
Preferably, step（2）The reaction temperature is 180 ~ 220 DEG C, and programming rate is 3 ~ 5 DEG C/min, soaking time 4
~6h。
Preferably, step（3）The nanometer spherical metal dust is copper powder, aluminium powder or the nickel powder that particle diameter is 30 ~ 80nm.
Preferably, step（3）The mixing quality ratio of presoma and the nanometer spherical metal dust is 10:2~20:1.
Preferably, step（3）It is heated at high temperature in the tube furnace, heating-up temperature is 700 ~ 1000 DEG C, the time is 1.5 ~
2.5h。
In the present invention, with the stabilization processes of organic carbon source, dehydration occurs between molecule, generates carbonyl and carbon
The functional groups such as carbon double bond, cause color gradually to be deepened.Because the speed of dehydration is slow, the stabilization processes time needs longer.
For anti-oxidation, should be handled at relatively low temperature and inert gas shielding., should be first ultrasonic when preparing composite precursor
Processing makes its dispersed mixing, and programming rate should be controlled rationally.It is organic during high-temperature heating thermally decomposes presoma
Carbon source molecule is occurred the Partial Elements such as various reactions, C, H, O such as rearrangement, cracking and removing is decomposed in the form of gas molecules, is gone out
Existing weightless and shrinkage phenomenon.If improving carburizing temperature, the initial charge specific capacity of obtained hard carbon material reduces, and discharge ratio first
Capacity first increases and then decreases, first charge-discharge efficiency are in increase trend.Because gained hard carbon material is a kind of amorphous carbon material,
Its structure keeps the class elliposoidal structure of original polymer.When carburizing temperature is relatively low, the degree of disorder of the spherical hard carbon of gained is higher,
Lithium storage content is larger, therefore initial charge specific capacity is higher, but the less stable of material, initial charge irreversible capacity compared with
Greatly.When carburizing temperature is higher, the degree of order of hard carbon improves, and lithium storage content reduces, and its stability and first charge-discharge efficiency have
Improved.Therefore, for the preferable hard carbon product of charge specific capacity, charge efficiency and stability is made, carbonization should rationally be controlled
Temperature and time.
It is and existing the invention provides a kind of preparation method of hard carbon/graphene composite negative pole for lithium battery
The characteristics of technology is compared, and it is protruded and excellent effect are：
1. hard carbon/graphene composite negative pole prepared by the present invention, the metal dust being coated in hard carbon can improve hard carbon
The electron mobility and electrical conductivity of microballoon, and spheroidal particle combination can improve the tap density of material, so as to lift electrode
Capacity.
2. hard carbon/graphene composite negative pole prepared by the present invention, spherical hard carbon coats metal dust, is clipped in stratiform stone
Between black alkene, due to this special sandwich construction, the defects of reversible specific capacity loss is larger is overcome.
3. hard carbon/graphene composite negative pole prepared by the present invention, its lithium battery assembled, stability is preferable,
Cycle performance is preferable.
4. the preparation method of the present invention, equipment is simple, and operating process is easy to control, and properties of product are stable, and cost performance is higher.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it prepares the tool of composite negative pole material
Body process is as follows：
Starch is placed in corundum crucible, then crucible is placed in tube type resistance furnace, under nitrogen atmosphere protection, rise temperature is extremely
240 DEG C, 10min stabilization processes are carried out to starch, make dehydration occurs between its molecule；By 1kg sheet graphenes
It is added to the starch after 2kg processing in 3.9kg ethanol, is sufficiently stirred and is uniformly dispersed, adds 1kg sodium metaaluminates and sodium hydroxide
Mixed liquor, the mass concentration of sodium metaaluminate is 0.5%, and the mass concentration of sodium hydroxide is 1%, is aged 2h at room temperature, then
Move into using polytetrafluoroethylene (PTFE) in the pyroreaction kettle of substrate, first to use supersound process 50min of the frequency for 80kHz, then with 4
DEG C/min speed is warming up to 180 DEG C, and is incubated 6h, it is swelled cross-linked structure special in starch, then filtered, first
Alcoholic solution is washed and dried, and obtains hard carbon/graphene presoma；It is receiving for 70nm by the presoma obtained by 1kg and 0.2kg particle diameters
Rice copper powder is well mixed in V-Mixer, is then charged into corundum crucible, under the protection of nitrogen atmosphere, in tube furnace
It is heated at high temperature to 950 DEG C of carburizing reagent 2.5h, thermally decomposes hard carbon presoma, forms spherical hard carbon and be coated on copper nanoparticle
Surface, and be clipped between lamellar graphite alkene, produce hard carbon/graphene composite negative pole.
Hard carbon/the graphene composite negative pole obtained to embodiment 1, lithium battery assembling is used it for, its 10C is tested and fills
Discharge capacitance, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Embodiment 2
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it prepares the tool of composite negative pole material
Body process is as follows：
Sucrose is placed in corundum crucible, then crucible is placed in tube type resistance furnace, under argon atmosphere protection, rise temperature is extremely
200 DEG C, 15min stabilization processes are carried out to sucrose, make dehydration occurs between its molecule；By 1kg sheet graphenes
It is added to the sucrose after 3kg processing in 5.2kg glycerine, is sufficiently stirred and is uniformly dispersed, adds 1.3kg sodium metaaluminates and hydrogen-oxygen
Change the mixed liquor of sodium, the mass concentration of sodium metaaluminate is 1%, and the mass concentration of sodium hydroxide is 2%, is aged 1.5h at room temperature,
Then move into using polytetrafluoroethylene (PTFE) in the pyroreaction kettle of substrate, first to use supersound process 40min of the frequency for 80kHz, then
200 DEG C are warming up to 5 DEG C/min speed, and is incubated 5h, cross-linked structure special in sucrose is swelled, then passes through
Filter, methanol solution are washed and dried, and obtain hard carbon/graphene presoma；It is by the presoma obtained by 2kg and 0.2kg particle diameters
40nm nanometer aluminium powder is well mixed in V-Mixer, is then charged into corundum crucible, under the protection of argon atmosphere, in
It is heated at high temperature to 1000 DEG C of carburizing reagent 1.5h in tube furnace, thermally decomposes hard carbon presoma, forms spherical hard carbon cladding
In the surface of nanometer aluminium powder, and it is clipped between lamellar graphite alkene, produces hard carbon/graphene composite negative pole.
Hard carbon/the graphene composite negative pole obtained to embodiment 2, lithium battery assembling is used it for, its 10C is tested and fills
Discharge capacitance, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Embodiment 3
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it prepares the tool of composite negative pole material
Body process is as follows：
Starch is placed in corundum crucible, then crucible is placed in tube type resistance furnace, under nitrogen atmosphere protection, rise temperature is extremely
230 DEG C, 12min stabilization processes are carried out to starch, make dehydration occurs between its molecule；By 1kg sheets graphene with
Starch after 2.5kg processing is added in 4.6kg ethanol, is sufficiently stirred and is uniformly dispersed, and adds 1.2kg sodium metaaluminates and hydroxide
The mixed liquor of sodium, the mass concentration of sodium metaaluminate is 0.5%, and the mass concentration of sodium hydroxide is 1%, is aged 1h at room temperature, so
Move into afterwards using polytetrafluoroethylene (PTFE) in the pyroreaction kettle of substrate, first to use supersound process 60min of the frequency for 80kHz, then with 3
DEG C/min speed is warming up to 190 DEG C, and is incubated 4h, it is swelled cross-linked structure special in starch, then filtered, first
Alcoholic solution is washed and dried, and obtains hard carbon/graphene presoma；It is receiving for 60nm by the presoma obtained by 1kg and 0.2kg particle diameters
Rice nickel powder is well mixed in V-Mixer, is then charged into corundum crucible, under the protection of nitrogen atmosphere, in tube furnace
It is heated at high temperature to 850 DEG C of carburizing reagent 2h, thermally decomposes hard carbon presoma, forms spherical hard carbon and be coated on nano-nickel powder
Surface, and be clipped between lamellar graphite alkene, produce hard carbon/graphene composite negative pole.
Hard carbon/the graphene composite negative pole obtained to embodiment 3, lithium battery assembling is used it for, its 10C is tested and fills
Discharge capacitance, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Embodiment 4
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it prepares the tool of composite negative pole material
Body process is as follows：
Sucrose is placed in corundum crucible, then crucible is placed in tube type resistance furnace, under argon atmosphere protection, rise temperature is extremely
210 DEG C, 10min stabilization processes are carried out to sucrose, make dehydration occurs between its molecule；By 1kg sheet graphenes
It is added to the sucrose after 2.2kg processing in 4.2kg methanol, is sufficiently stirred and is uniformly dispersed, adds 1.1kg sodium metaaluminates and hydrogen-oxygen
Change the mixed liquor of sodium, the mass concentration of sodium metaaluminate is 1%, and the mass concentration of sodium hydroxide is 2%, is aged 2h at room temperature, so
Move into afterwards using polytetrafluoroethylene (PTFE) in the pyroreaction kettle of substrate, first to use supersound process 50min of the frequency for 80kHz, then with 5
DEG C/min speed is warming up to 210 DEG C, and is incubated 4h, it is swelled cross-linked structure special in sucrose, then filtered, first
Alcoholic solution is washed and dried, and obtains hard carbon/graphene presoma；It is 50nm's by the presoma obtained by 1.2kg and 0.1kg particle diameters
Copper nanoparticle is well mixed in V-Mixer, is then charged into corundum crucible, under the protection of argon atmosphere, in tube furnace
Inside it is heated at high temperature to 800 DEG C of carburizing reagent 1.5h, thermally decomposes hard carbon presoma, forms spherical hard carbon and be coated on Nanometer Copper
The surface of powder, and be clipped between lamellar graphite alkene, produce hard carbon/graphene composite negative pole.
Hard carbon/the graphene composite negative pole obtained to embodiment 4, lithium battery assembling is used it for, its 10C is tested and fills
Discharge capacitance, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Embodiment 5
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it prepares the tool of composite negative pole material
Body process is as follows：
Sucrose is placed in corundum crucible, then crucible is placed in tube type resistance furnace, under nitrogen atmosphere protection, rise temperature is extremely
220 DEG C, 15min stabilization processes are carried out to sucrose, make dehydration occurs between its molecule；By 1kg sheet graphenes
It is added to the sucrose after 2.8kg processing in 4.9kg glycerine, is sufficiently stirred and is uniformly dispersed, adds 1.3kg sodium metaaluminates and hydrogen
The mixed liquor of sodium oxide molybdena, the mass concentration of sodium metaaluminate is 1%, and the mass concentration of sodium hydroxide is 2%, is aged at room temperature
1.5h, then move into using polytetrafluoroethylene (PTFE) in the pyroreaction kettle of substrate, first to use supersound process of the frequency for 80kHz
50min, then 190 DEG C are warming up to 4 DEG C/min speed, and 5h is incubated, it is swelled cross-linked structure special in sucrose, so
By filtering, methanol solution washing and dry, obtain hard carbon/graphene presoma；By the presoma obtained by 2kg and 0.15kg grains
The nanometer aluminium powder that footpath is 30nm is well mixed in V-Mixer, is then charged into corundum crucible, in the protection of nitrogen atmosphere
Under, in being heated at high temperature to 700 DEG C of carburizing reagent 1.5h in tube furnace, hard carbon presoma is thermally decomposed, forms spherical hard carbon
The surface of nanometer aluminium powder is coated on, and is clipped between lamellar graphite alkene, produces hard carbon/graphene composite negative pole.
Hard carbon/the graphene composite negative pole obtained to embodiment 5, lithium battery assembling is used it for, its 10C is tested and fills
Discharge capacitance, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Embodiment 6
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it prepares the tool of composite negative pole material
Body process is as follows：
Starch is placed in corundum crucible, then crucible is placed in tube type resistance furnace, under argon atmosphere protection, rise temperature is extremely
200 DEG C, 10min stabilization processes are carried out to starch, make dehydration occurs between its molecule；By 1kg sheet graphenes
It is added to the starch after 2.4kg processing in 4.4kg ethanol, is sufficiently stirred and is uniformly dispersed, adds 1.1kg sodium metaaluminates and hydrogen-oxygen
Change the mixed liquor of sodium, the mass concentration of sodium metaaluminate is 1%, and the mass concentration of sodium hydroxide is 1%, is aged 1h at room temperature, so
Move into afterwards using polytetrafluoroethylene (PTFE) in the pyroreaction kettle of substrate, first to use supersound process 40min of the frequency for 80kHz, then with 4
DEG C/min speed is warming up to 220 DEG C, and is incubated 4h, it is swelled cross-linked structure special in starch, then filtered, first
Alcoholic solution is washed and dried, and obtains hard carbon/graphene presoma；It is 60nm by the presoma obtained by 1.5kg and 0.18kg particle diameters
Nano-nickel powder in V-Mixer be well mixed, be then charged into corundum crucible, under the protection of argon atmosphere, in tubular type
Furnace high-temperature is heated to 900 DEG C of carburizing reagent 2h, thermally decomposes hard carbon presoma, forms spherical hard carbon and is coated on nano nickel
The surface of powder, and be clipped between lamellar graphite alkene, produce hard carbon/graphene composite negative pole.
Hard carbon/the graphene composite negative pole obtained to embodiment 6, lithium battery assembling is used it for, its 10C is tested and fills
Discharge capacitance, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Comparative example 1
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it prepares the tool of composite negative pole material
Body process is as follows：
Starch is placed in corundum crucible, then crucible is placed in tube type resistance furnace, under argon atmosphere protection, rise temperature is extremely
200 DEG C, 10min stabilization processes are carried out to starch, make dehydration occurs between its molecule；By 1kg sheet graphenes
It is added to the starch after 2.4kg processing in 4.4kg ethanol, is sufficiently stirred and is uniformly dispersed, adds 1.1kg sodium metaaluminates and hydrogen-oxygen
Change the mixed liquor of sodium, the mass concentration of sodium metaaluminate is 1%, and the mass concentration of sodium hydroxide is 1%, is aged 1h at room temperature, so
Move into afterwards using polytetrafluoroethylene (PTFE) in the pyroreaction kettle of substrate, first to use supersound process 40min of the frequency for 80kHz, then with 4
DEG C/min speed is warming up to 220 DEG C, and is incubated 4h, it is swelled cross-linked structure special in starch, then filtered, first
Alcoholic solution is washed and dried, and obtains hard carbon/graphene presoma；Presoma obtained by 1.5kg is mixed in V-Mixer
It is even, it is then charged into corundum crucible, under the protection of argon atmosphere, in being heated at high temperature to 900 DEG C of carburizing reagent 2h in tube furnace,
Hard carbon presoma is thermally decomposed, forms hard carbon, and is clipped between lamellar graphite alkene, produces hard carbon/graphene composite negative
Material.
Hard carbon/graphene composite negative pole that comparative example 1 obtains, lithium battery assembling is used it for, tests its 10C charge and discharge
Capacitance conservation rate, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Comparative example 2
A kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, it prepares the tool of composite negative pole material
Body process is as follows：
Starch is placed in corundum crucible, then crucible is placed in tube type resistance furnace, under argon atmosphere protection, rise temperature is extremely
200 DEG C, 10min stabilization processes are carried out to starch, make dehydration occurs between its molecule；By 1kg sheet graphenes
With 2.4kg processing after starch be added in 4.4kg ethanol, be sufficiently stirred and be uniformly dispersed, then move into using polytetrafluoroethylene (PTFE) as
In the pyroreaction kettle of substrate, supersound process 40min of the frequency for 80kHz is first used, then be warming up to 4 DEG C/min speed
220 DEG C, and 4h is incubated, then filtered, methanol solution is washed and dried, and obtains hard carbon/graphene presoma；By 1.5kg institutes
The presoma obtained is well mixed with the nano-nickel powder that 0.18kg particle diameters are 60nm in V-Mixer, is then charged into corundum crucible
In, under the protection of argon atmosphere, in being heated at high temperature to 900 DEG C of carburizing reagent 2h in tube furnace, make hard carbon presoma that heat occur
Decompose, form hard carbon and be coated on the surface of nano-nickel powder, and be clipped between lamellar graphite alkene, produce hard carbon/graphene Compound Negative
Pole material.
Hard carbon/graphene composite negative pole that comparative example 2 obtains, lithium battery assembling is used it for, tests its 10C charge and discharge
Capacitance conservation rate, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Pasty state gluing is made in the obtained negative material of embodiment 1-6, comparative example 1-2 and butadiene-styrene rubber, aqueous binder
Agent, even application roll-in, are cut, into negative plate in copper foil both sides；Assembled for lithium battery, test its 10C charge/discharge capacity guarantor
Holdup, first discharge capacity, first coulombic efficiency.Obtained data are as shown in table 1.
Table 1：
From table 1：
The lithium battery assembled using hard carbon/graphene composite negative pole made from the method for the present invention, is not had with comparative example 1
Tangible glomeration hard carbon is coated on the negative pole of nano metal, the negative pole of 2 imperfect hard carbon of comparative example cladding is compared, first charge-discharge
Conservation rate, first discharge capacity and coulombic efficiency is improved first, illustrate to improve hard carbon microballoon with nano metal powder
Electron mobility and electrical conductivity, and spheroidal particle combines and improves the tap density of material, so as to improve the capacity of electrode,
And the presence of graphene improves the reversible specific capacity of composite, therefore cycle performance is also improved.
Claims (8)
1. a kind of preparation method of hard carbon/graphene composite negative pole for lithium battery, is characterized in carrying out organic carbon source
After stabilization processes, it is mixed in sheet graphene in organic solvent, temperature reaction after supersound process, obtains hard carbon graphite
The composite precursor of alkene；Then presoma is mixed with nanometer spherical metal dust, high warm is carried out under inert gas shielding
Decompose, form spherical hard carbon and be coated on the surface of nanometer spherical metal dust, and be clipped between lamellar graphite alkene, produce hard carbon/
Graphene composite negative pole；What is prepared comprises the following steps that：
（1）Organic carbon source is placed in corundum crucible, then crucible is placed in tube type resistance furnace, is protected in atmosphere of inert gases
Under, temperature is raised, the stabilization processes of certain time are carried out to organic carbon source, make dehydration occurs between its molecule；
（2）By sheet graphene and step（1）The organic carbon source of processing is added in organic solvent, is sufficiently stirred scattered equal
It is even, the mixed liquor of a certain amount of sodium metaaluminate and sodium hydroxide is added, 1 ~ 2h is aged at room temperature, then moves into polytetrafluoroethyl-ne
Alkene is in the pyroreaction kettle of substrate, is first ultrasonically treated certain time, then is gradually heating to reaction temperature, and is incubated a timing
Between, it is swelled organic carbon source, then filtered, methanol solution is washed and dried, and obtains hard carbon/graphene presoma；
（3）By step（2）The presoma of gained is well mixed with nanometer spherical metal dust in V-Mixer, is then charged into
In corundum crucible, under the protection of atmosphere, in being heated at high temperature in tube furnace, hard carbon presoma is thermally decomposed, formed
Spherical hard carbon is coated on the surface of nano metal powder, and is clipped between lamellar graphite alkene, produces hard carbon/graphene composite negative
Material.
2. the preparation method of a kind of hard carbon/graphene composite negative pole for lithium battery according to claim 1, it is special
Sign is：Step（1）The organic carbon source starch or sucrose.
3. the preparation method of a kind of hard carbon/graphene composite negative pole for lithium battery according to claim 1, it is special
Sign is：Step（1）The treatment temperature is 200 ~ 240 DEG C, processing time 10-15min.
4. the preparation method of a kind of hard carbon/graphene composite negative pole for lithium battery according to claim 1, it is special
Sign is：Step（2）The number of plies of the sheet graphene is less than 5 layers, and the mass ratio of itself and the organic carbon source of processing is 1:3
~1:2；The organic solvent is methanol, ethanol or glycerine, and its addition is graphene and the organic carbon source quality summation of processing
1.2 ~ 1.5 times.
5. the preparation method of a kind of hard carbon/graphene composite negative pole for lithium battery according to claim 1, it is special
Sign is：Step（2）In the mixed liquor, the mass concentration of sodium metaaluminate is 0.5 ~ 1%, the mass concentration of sodium hydroxide for 1 ~
2%, the addition quality of mixed liquor is the 1/4 ~ 1/3 of organic solvent quality.
6. the preparation method of a kind of hard carbon/graphene composite negative pole for lithium battery according to claim 1, it is special
Sign is：Step（2）The power of the supersound process is 80kHz, and the time is 40 ~ 60min；The reaction temperature is 180 ~ 220
DEG C, programming rate is 3 ~ 5 DEG C/min, and soaking time is 4 ~ 6h.
7. the preparation method of a kind of hard carbon/graphene composite negative pole for lithium battery according to claim 1, it is special
Sign is：Step（3）The nanometer spherical metal dust is copper powder, aluminium powder or the nickel powder that particle diameter is 30 ~ 80nm；The presoma
Mixing quality ratio with nanometer spherical metal dust is 10:2~20:1.
8. the preparation method of a kind of hard carbon/graphene composite negative pole for lithium battery according to claim 1, it is special
Sign is：Step（3）It is heated at high temperature in the tube furnace, heating-up temperature is 700 ~ 1000 DEG C, and the time is 1.5 ~ 2.5h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108777303A (en) * | 2018-05-29 | 2018-11-09 | 武汉工程大学 | A kind of biomass derived hard carbon/graphene anode material of lithium-ion battery and preparation method thereof |
| CN109192984A (en) * | 2018-08-24 | 2019-01-11 | 宁波科力安新能源技术有限公司 | A kind of lithium battery |
| CN109950539A (en) * | 2019-03-15 | 2019-06-28 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of preparation method of graphene coated carbon negative pole material |
| CN110247054A (en) * | 2019-06-28 | 2019-09-17 | 蜂巢能源科技有限公司 | Composite cathode material of silicon/carbon/graphite and preparation method thereof, battery |
| CN110364690A (en) * | 2018-04-09 | 2019-10-22 | 微宏动力系统（湖州）有限公司 | Preparation method, negative electrode material and the lithium battery of negative electrode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683657A (en) * | 2012-05-11 | 2012-09-19 | 常州第六元素材料科技股份有限公司 | Graphene composite material for cathode of lithium ion battery and preparation method of graphene composite material |
| CN103050661A (en) * | 2012-12-12 | 2013-04-17 | 清华大学深圳研究生院 | Lithium ion battery cathode material compounded with graphene and preparation method thereof |
| CN105161721A (en) * | 2015-08-04 | 2015-12-16 | 天津大学 | Three-dimensional composite material formed by filling carbon-encapsulated tin granules into graphene interlaminations and by filling graphene layers with carbon-encapsulated tin granules and preparation method for three-dimensional composite material |
| CN106910894A (en) * | 2017-04-12 | 2017-06-30 | 西安理工大学 | A kind of preparation method of mesoporous nano carbon microspheres graphene interlayers composite |
-
2017
- 2017-10-20 CN CN201710984589.7A patent/CN107732245B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683657A (en) * | 2012-05-11 | 2012-09-19 | 常州第六元素材料科技股份有限公司 | Graphene composite material for cathode of lithium ion battery and preparation method of graphene composite material |
| CN103050661A (en) * | 2012-12-12 | 2013-04-17 | 清华大学深圳研究生院 | Lithium ion battery cathode material compounded with graphene and preparation method thereof |
| CN105161721A (en) * | 2015-08-04 | 2015-12-16 | 天津大学 | Three-dimensional composite material formed by filling carbon-encapsulated tin granules into graphene interlaminations and by filling graphene layers with carbon-encapsulated tin granules and preparation method for three-dimensional composite material |
| CN106910894A (en) * | 2017-04-12 | 2017-06-30 | 西安理工大学 | A kind of preparation method of mesoporous nano carbon microspheres graphene interlayers composite |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364690A (en) * | 2018-04-09 | 2019-10-22 | 微宏动力系统（湖州）有限公司 | Preparation method, negative electrode material and the lithium battery of negative electrode material |
| CN108777303A (en) * | 2018-05-29 | 2018-11-09 | 武汉工程大学 | A kind of biomass derived hard carbon/graphene anode material of lithium-ion battery and preparation method thereof |
| CN109192984A (en) * | 2018-08-24 | 2019-01-11 | 宁波科力安新能源技术有限公司 | A kind of lithium battery |
| CN109950539A (en) * | 2019-03-15 | 2019-06-28 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of preparation method of graphene coated carbon negative pole material |
| CN110247054A (en) * | 2019-06-28 | 2019-09-17 | 蜂巢能源科技有限公司 | Composite cathode material of silicon/carbon/graphite and preparation method thereof, battery |
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